CN103354950B - Hermetic sealing cap material, electronic unit storage container and the manufacture method of hermetic sealing cap material - Google Patents

Hermetic sealing cap material, electronic unit storage container and the manufacture method of hermetic sealing cap material Download PDF

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Publication number
CN103354950B
CN103354950B CN201180066844.0A CN201180066844A CN103354950B CN 103354950 B CN103354950 B CN 103354950B CN 201180066844 A CN201180066844 A CN 201180066844A CN 103354950 B CN103354950 B CN 103354950B
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China
Prior art keywords
layer
metal base
sealing cap
hermetic sealing
electronic unit
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Expired - Fee Related
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CN201180066844.0A
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Chinese (zh)
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CN103354950A (en
Inventor
山本雅春
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Proterial Ltd
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Hitachi Metals Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/02—Containers; Seals
    • H01L23/04—Containers; Seals characterised by the shape of the container or parts, e.g. caps, walls
    • H01L23/053—Containers; Seals characterised by the shape of the container or parts, e.g. caps, walls the container being a hollow construction and having an insulating or insulated base as a mounting for the semiconductor body
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/02—Containers; Seals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/02—Containers; Seals
    • H01L23/10—Containers; Seals characterised by the material or arrangement of seals between parts, e.g. between cap and base of the container or between leads and walls of the container
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/161—Cap
    • H01L2924/1615—Shape
    • H01L2924/16195—Flat cap [not enclosing an internal cavity]
    • H—ELECTRICITY
    • H03—ELECTRONIC CIRCUITRY
    • H03H—IMPEDANCE NETWORKS, e.g. RESONANT CIRCUITS; RESONATORS
    • H03H9/00—Networks comprising electromechanical or electro-acoustic devices; Electromechanical resonators
    • H03H9/02—Details
    • H03H9/05—Holders; Supports
    • H03H9/10—Mounting in enclosures
    • H03H9/1007—Mounting in enclosures for bulk acoustic wave [BAW] devices
    • H03H9/1014—Mounting in enclosures for bulk acoustic wave [BAW] devices the enclosure being defined by a frame built on a substrate and a cap, the frame having no mechanical contact with the BAW device

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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Piezo-Electric Or Mechanical Vibrators, Or Delay Or Filter Circuits (AREA)

Abstract

The present invention provides the glass material used without Pb, can substantially ensure that the bubble-tight hermetic sealing cap material of electronic unit storage container.This hermetic sealing cap material (1,201) possesses: the metal base (12,212) comprising the metal material at least containing Cr；The clad (13,213a, 213b) being made up of the oxide film thereon of Cr formed on the surface of metal base；Formed on the surface of clad is made up of the glass material without Pb and for engaging the bonding layer (11) of metal base and electronic unit storage component (30) being formed with clad.

Description

Hermetic sealing cap material, electronic unit storage container and hermetic sealing cap material Manufacture method
Technical field
The present invention relates to hermetic sealing cap material, electronic unit storage container (package) and hermetic sealing cap material Manufacture method.
Background technology
At present it is known that a kind of electronic unit storage container, it uses the joint being made up of the solder containing Pb or glass Layer, by lid material with the electronic unit storage component being made up of ceramic material to be accommodated with the state gas-tight seal of electronic unit.But It is to use containing the solder of Pb or glass in electronic unit storage container, the most preferred because Pb is harmful substance, it is desirable to Grafting material without Pb.
Additionally, in the case of lid material uses ceramic material, the thickness of lid material becomes big, thus electronic unit storage can be produced and use The unfavorable condition that container maximizes.It is therefore desirable to use the metal material work that can more reduce lid material thickness than ceramic material For lid material.
Here, motion has a kind of electronic unit storage container, it uses by connecing that the Au-20Sn alloy without Pb is constituted Close layer, the lid material that gas-tight seal is made up of and the electronic unit storage component being made up of ceramic material metal material.This Au-20Sn Alloy is because of fusing point low (about 280 DEG C), it is possible to the electronic unit that suppression is received deteriorates because of heat.But, Au holds high Expensive, therefore it is required that there is the substitution material of Au-20Sn alloy.
In view of above-mentioned situation, current motion has a kind of electronic unit storage container, and its use is not to be closed by Au-20Sn Gold but the bonding layer that is made up of glass material, the lid material that gas-tight seal is made up of metal material and the electricity being made up of ceramic material Subassembly storage component.Such electronic unit storage container is such as disclosed in Japanese Unexamined Patent Publication 2002-26679 publication.
Above-mentioned Japanese Unexamined Patent Publication 2002-26679 publication discloses the quartz crystal (electronic unit of a kind of surface installing type Storage container), it possesses quartz crystal, includes the recess for receiving quartz crystal and the frame portion formed around recess Ceramic vessel and crown cap.The crown cap of the quartz crystal of this surface installing type, by Fe system alloy (the section watt ferrum containing plating Ni Base nickel cobalt (alloy) (Kovar)) or Fe system alloy (426 alloy) containing the Ni of 42 mass % and Cr and Fe of 6 mass % constitute. In surface-mounted crystal oscillator, the frame portion of ceramic vessel and crown cap are engaged by low-melting glass, thus, and quartz crystal quilt It is hermetically sealed in ceramic vessel.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2002-26679 publication
Summary of the invention
Invent problem to be solved
But, the quartz crystal of the surface installing type disclosed in above-mentioned Japanese Unexamined Patent Publication 2002-26679 publication, crown cap It is made up of Ni plating Fe system alloy (section watt iron-based nickel cobalt (alloy)), 426 alloys, therefore, the metal level on crown cap surface and low melting point Glass likely can not be the most closely sealed.In this case, can exist cannot substantially ensure that surface installing type quartz crystal (pottery Porcelain container) bubble-tight problem.
The present invention makes to solve above-mentioned problem, it is an object of the present invention to provide a kind of use and does not contains The glass material of Pb, it is possible to substantially ensure that the bubble-tight hermetic sealing cap material of electronic unit storage container, electronic unit Storage container and the manufacture method of hermetic sealing cap material.
The effect of method and invention for solving problem
The hermetic sealing cap material of a first aspect of the present invention, include being made up of ceramic material for housing electronic portion Using in the electronic unit storage container of the electronic unit storage component of part, this hermetic sealing cap material possesses: comprise at least The metal base of the metal material containing Cr；The cladding being made up of the oxide film thereon of Cr formed on the surface of metal base Layer；With on the surface of clad formed be made up of the glass material without Pb and for engage be formed with clad Metal base receives the bonding layer of component with electronic unit.
The hermetic sealing cap material of a first aspect of the present invention, as it has been described above, by possessing on the surface of metal base The clad being made up of the oxide film thereon of Cr formed；With on the surface of clad formed by the glass material structure without Pb Become and for engaging the bonding layer of metal base and the electronic unit storage component being formed with clad such that it is able to make structure The oxide film thereon becoming the Cr of clad is the most closely sealed with the glass material constituting bonding layer, therefore, and metal base and electronic unit Storage component can be sufficiently engaged with.Thus, the glass material without Pb is used, it is possible to substantially ensure that electronic unit storage container Air-tightness.Additionally, by possessing the metal base comprising the metal material at least containing Cr, use ceramic material with base material Situation is compared, it is possible to reduce the thickness of hermetic sealing cap material, therefore, it is possible to the maximization of suppression electronic unit storage container. Additionally, metal base comprises the metal material at least containing Cr, thus, the surface of metal base can easily be formed by Cr Oxide film thereon constitute clad.
The hermetic sealing cap material of above-mentioned first aspect, is preferably configured as: the temperature range of less than 250 DEG C more than 30 DEG C In, the thermalexpansioncoefficientα 1(of bonding layer/DEG C) and metal base thermalexpansioncoefficientα 2(/ DEG C) meet-15 × 10-7≤α2-α1 ≤5×10-7Relation.According to such composition, when jointing metal base material reduces temperature with temperature during bonding layer, it is possible to subtract The stress that the little bonding layer being made up of glass material produces, therefore, it is possible to suppress to produce in the bonding layer being made up of glass material Rupture (slight crack).
In the hermetic sealing cap material of above-mentioned first aspect, the preferably thickness of clad is more than 0.3 μm.According to such Constitute, it is possible to substantially ensure that the thickness of clad, therefore, it is possible to make Cr oxide film thereon and the composition bonding layer of composition clad Glass material is the most closely sealed.
The hermetic sealing cap material of above-mentioned first aspect, preferably metal base comprise containing more than Ni, 3 mass % 6 mass % The Fe system alloy of following Cr and Fe.According to such composition, metal base is by the Fe system alloy containing Cr more than 3 mass % Constitute, thereby, it is possible to be reliably formed the clad being made up of the oxide film thereon of Cr on the surface of metal base.It addition, it is logical Cross metal base to be made up of the Fe system alloy containing the Cr below 6 mass %, it is possible to the metal that suppression causes because of the superfluous content of Cr The thermal coefficient of expansion of base material increases, and can suppress the notable of the thermal coefficient of expansion of metal base and the thermal coefficient of expansion of bonding layer Difference.Thereby, it is possible to suppression produces by rupturing that the difference of thermal expansion produces in bonding layer or metal base.It addition, Metal base contains Ni, it is possible to reduce the thermal coefficient of expansion of metal base, accordingly, it is capable to make the thermal coefficient of expansion of metal base more Thermal coefficient of expansion close to the bonding layer being made up of the glass material less than the thermal coefficient of expansion of general metal material.
In this case, preferably metal base by the Cr below more than the Ni containing 42 mass %, 3 mass % 6 mass % and The Fe system alloy of Fe is constituted.According to such composition, metal base contains the Ni of 42 mass %, can reliably reduce metal base Thermal coefficient of expansion, therefore, it is possible to make the thermal coefficient of expansion of metal base reliably close to by the little glass material of thermal coefficient of expansion The thermal coefficient of expansion of the bonding layer that material is constituted.It addition, metal base by more than the Ni containing 42 mass %, 3 mass % 6 mass % with Under the Fe system alloy of Cr constitute, thus, may be configured as thermalexpansioncoefficientα 1 and the thermalexpansioncoefficientα of metal base of bonding layer 2 disclosure satisfy that-15 × 10-7≤α2-α1≤5×10-7Relation, therefore, it is possible to reliably suppress the joint being made up of glass material Produce in Ceng and rupture.Additionally, inventor herein is for above-mentioned viewpoint, complete confirmation by test.
In the hermetic sealing cap material of above-mentioned first aspect, preferably clad is formed at the metal base of configuration bonding layer On surface and with configuration tielayer side opposition side metal base surface on.According to such composition, and only in Metal Substrate The situation forming clad on any one face in two surfaces of material is different, it is possible to prevent from being formed without the Metal Substrate of clad Form bonding layer on the surface of material by mistake.
In the hermetic sealing cap material of above-mentioned first aspect, preferably metal base is arranged in tielayer side, by least including Compound (clad) material of the ground floor and the second layer containing the metal material different from ground floor that at least contain Cr is constituted.Root According to such composition, with metal base only compared with 1 layer of situation about constituting, the variety classes different by engaging thermal coefficient of expansion Metal material each other, it is possible to be easily adjusted the thermal coefficient of expansion of metal base.It addition, at least contain Cr in tielayer side configuration Ground floor, thus, corresponding to formed bonding layer region metal base surface on can easily be formed by the oxygen of Cr Change the clad that tunicle is constituted.
In this case, preferably the thermal coefficient of expansion of ground floor is more than the thermal coefficient of expansion of bonding layer, and the heat of the second layer is swollen Swollen coefficient is less than the thermal coefficient of expansion of bonding layer.According to such composition, by adjusting thickness and the thickness of the second layer of ground floor Degree, it is possible to make the thermal coefficient of expansion as metal base entirety close to the thermal coefficient of expansion of bonding layer.
At the hermetic sealing cap material that above-mentioned metal base is made up of the composite at least including ground floor and the second layer In, the preferably ground floor of metal base is made up of the Fe system alloy containing Cr and Fe below more than Ni, 3 mass % 6 mass %. According to such composition, the surface of the metal base in the region corresponding to forming bonding layer can be reliably formed by the oxygen of Cr Change the clad that tunicle is constituted.It addition, the ground floor of metal base is made up of the Fe system alloy containing Ni, it is possible to reduce The thermal coefficient of expansion of one layer, thus, it is possible to make the close glass material little by thermal coefficient of expansion of thermal coefficient of expansion of metal base The thermal coefficient of expansion of the bonding layer constituted.
At the hermetic sealing cap material that above-mentioned metal base is made up of the composite at least including ground floor and the second layer In, preferably metal base is made up of the composite including following layers: be arranged in the ground floor at least containing Cr of tielayer side； It is arranged in ground floor with bonding layer opposition side, comprises the second layer of the metal material different from ground floor；Be arranged in The opposition side with ground floor of two layers, at least contains the third layer of Cr.According to such composition, it is positioned at the face side of metal base Ground floor and third layer be each configured at least contain Cr, therefore, it is possible to metal base two surfaces (ground floor with The face of the opposition side of the second layer and the face of the opposition side with the second layer of third layer) on formed respectively and be made up of the oxide film thereon of Cr Clad.It is so, different from the situation being formed with clad on only any one face in two surfaces of metal base, it is possible to Prevent from being formed bonding layer on the surface of metal base being formed without clad by mistake.
At the hermetic sealing cap that above-mentioned metal base is made up of the composite including ground floor, the second layer and third layer In material, preferably ground floor and third layer are by the Fe system alloy structure containing Cr and Fe below more than Ni, 3 mass % 6 mass % Become.According to such composition, ground floor and third layer by metal base are constituted by the Fe system alloy containing Ni, it is possible to subtract Little ground floor and the thermal coefficient of expansion of third layer.Thereby, it is possible to make as the thermal coefficient of expansion that metal base is overall close by heat The thermal coefficient of expansion of the bonding layer that the glass material that the coefficient of expansion is little is constituted.
In the hermetic sealing cap material that above-mentioned ground floor and third layer are made up of Fe system alloy, preferably ground floor and the 3rd Layer is constituted by the Fe system alloy of the Ni containing 42 mass %, Cr and Fe of 6 mass %, the second layer by the Ni containing 42 mass %, Constitute with the Fe system alloy of Fe.According to such composition, by the ground floor of metal base, the second layer and third layer by containing The Fe system alloy of the Ni of 42 mass % is constituted, it is possible to reliably reduce the thermal coefficient of expansion of ground floor, the second layer, third layer.By This, it is possible to make the thermal coefficient of expansion thermal expansion close to the bonding layer being made up of the glass material that thermal coefficient of expansion is little of metal base Coefficient.It addition, ground floor and third layer are by the Ni containing 42 mass %, the common Fe system alloy structure of Cr and Fe of 6 mass % Becoming, the second layer is made up of the common Fe system alloy of Ni and Fe containing 42 mass %, thereby, it is possible to use the Fe being readily available It is alloy, the surface of the metal base in the region corresponding to being formed with bonding layer forms the bag being made up of the oxide film thereon of Cr Coating, and the thermal coefficient of expansion thermal coefficient of expansion close to the bonding layer being made up of glass material of metal base can be made.
In the hermetic sealing cap material that above-mentioned ground floor and third layer are made up of Fe system alloy, preferably ground floor and the 3rd The aggregate thickness of layer is more than the 50% of the thickness of metal base entirety.According to such composition, then can be configured to bonding layer The thermalexpansioncoefficientα 2 of thermalexpansioncoefficientα 1 and metal base meets-15 × 10-7≤α2-α1≤5×10-7Relation, therefore, Can reliably prevent from the bonding layer being made up of glass material from producing to rupture.Inventor herein for this point also by experiment Complete confirmation.
The electronic unit storage container of a second aspect of the present invention, possesses hermetic sealing cap material and electronic unit storage Component, wherein, above-mentioned hermetic sealing cap material includes: have the metal base of the metal material at least containing Cr, in Metal Substrate On the surface of material formed the clad being made up of the oxide film thereon of Cr, and on the surface of clad formed by the glass without Pb The bonding layer that glass material is constituted；Above-mentioned electronic unit storage component engages with the metal base being formed with clad via bonding layer And it is made up of ceramic material, for housing electronic parts.
The electronic unit storage container of a second aspect of the present invention, as it has been described above, hermetic sealing cap material includes: at gold Belong to base material surface on formed the clad being made up of the oxide film thereon of Cr, formed in cover surface by without Pb's Glass material constitute bonding layer, and electronic unit storage component be configured to via bonding layer and the metal being formed with clad Base material engages, thereby, it is possible to make the oxide film thereon of the Cr of composition clad and the glass material constituting bonding layer the most closely sealed, because of This, metal base can be sufficiently engaged with electronic unit storage component.Thereby, it is possible to use the glass material without Pb, fully Guarantee the air-tightness of electronic unit storage container.It addition, hermetic sealing cap material, including having the metal material at least containing Cr The metal base of material, thus, compared with the situation that base material uses ceramic material, it is possible to reduce the thickness of hermetic sealing cap material, Therefore, it is possible to the maximization of suppression electronic unit storage container.It addition, had the metal at least containing Cr by metal base Material, it is possible to easily form the clad being made up of the oxide film thereon of Cr on the surface of metal base.
In the electronic unit storage container of above-mentioned second aspect, it is preferably configured as the temperature of less than 250 DEG C more than 30 DEG C In degree scope, the thermalexpansioncoefficientα 1(of bonding layer/DEG C) and electronic unit storage component thermalexpansioncoefficientα 3(/ DEG C) meet 0 ≤α1-α3≤10×10-7Relation.According to such composition, receive temperature when component engages from bonding layer and electronic unit When reducing temperature, it is possible to reduce the stress produced in the bonding layer being made up of glass material, therefore, it is possible to suppression is by glass material The bonding layer constituted produces and ruptures (slight crack).
In this case, it is preferably configured as more than 30 DEG C in the temperature range of less than 250 DEG C, the thermal expansion system of bonding layer Number α 1(/ DEG C) and electronic unit storage component thermalexpansioncoefficientα 3(/ DEG C) satisfied 0≤α 1-α 3≤10 × 10-7Relation, and And, the thermalexpansioncoefficientα 1(of bonding layer/DEG C) and metal base thermalexpansioncoefficientα 2(/ DEG C) meet-15 × 10-7≤α2-α1 ≤5×10-7Relation.According to such composition, by for 0≤α 1-α 3≤10 × 10-7, it is possible to it is configured to the electricity at bonding layer Subassembly storage member side does not apply stress or somewhat applies tensile stress.Additionally, by for-15 × 10-7≤α2-α1≤5 ×10-7, it is possible to the metal base side being formed in bonding layer does not apply stress or somewhat applies tensile stress.Thus, though In the case of bonding layer is applied stress, also receive the bonding layer of configuration between component at metal base and electronic unit, execute Add the tensile stress receiving component from metal base and electronic unit, therefore, and only from metal base and electronic unit The situation that any one in storage component applies stress to bonding layer is different, can suppress to produce in the bonding layer to rupture.
The manufacture method of the hermetic sealing cap material of a third aspect of the present invention, including being made up of ceramic material, The hermetic sealing cap material used in the electronic unit storage container of component is received for the electronic unit of housing electronic parts Manufacture method, it possesses: by making metal base on the surface of the metal base comprising the metal material at least containing Cr Cr oxidation, and form the operation of clad being made up of the oxide film thereon of Cr；With in cover surface, formed by without Pb Glass material constitute and for engaging the bonding layer being formed with the metal base of clad with electronic unit storage component Operation.
The manufacture method of the hermetic sealing cap material of a third aspect of the present invention, as it has been described above, possess: by comprise to The Cr oxidation of metal base is made to be formed by the oxide film thereon structure of Cr on the surface of the metal base containing the metal material of Cr less The operation of the clad become；With in cover surface, formed be made up of the glass material without Pb and for engaging shape Become to have metal base and the operation of the bonding layer of electronic unit storage component of clad, thus, constitute the oxygen of the Cr of clad Changing tunicle can be the most closely sealed with the glass material constituting bonding layer, and therefore metal base can fill with electronic unit storage component Tap is closed.Thereby, it is possible to use the glass material without Pb, substantially ensure that the air-tightness of electronic unit storage container.Additionally, The metal base of the metal material at least containing Cr is comprised by use, compared with the situation using ceramic material in base material, energy Enough reduce the thickness of hermetic sealing cap material, therefore, it is possible to the maximization of suppression electronic unit storage container.Additionally, metal Base material comprises the metal material at least containing Cr, thereby, it is possible to easily formed by the oxidation quilt of Cr on the surface of metal base The clad that film is constituted.
In the manufacture method of the hermetic sealing cap material of the above-mentioned third aspect, the operation being preferably formed as clad includes: Comprise the metal base of the metal material of the Fe system alloy with Cr and Fe below containing more than Ni and 3 mass % 6 mass % The operation of the clad being made up of the oxide film thereon of Cr is formed on surface.According to such composition, metal base is by containing 3 matter The Fe system alloy of the Cr of amount more than % is constituted, thereby, it is possible to be reliably formed on the surface of metal base by the oxide film thereon structure of Cr The clad become.Additionally, be made up of the Fe system alloy containing the Cr below 6 mass % by metal base, it is possible to suppression is because of Cr's The thermal coefficient of expansion of the metal base that superfluous content causes increases, and the thermal coefficient of expansion of suppression metal base and the heat of bonding layer are swollen Swollen coefficient is dramatically different.Thereby, it is possible to suppression produces by rupturing that the difference of thermal expansion causes in bonding layer or metal base (slight crack) etc..Additionally, metal base contains Ni, thereby, it is possible to reduce the thermal coefficient of expansion of metal base, it is possible to make metal base Thermal coefficient of expansion close to the thermal coefficient of expansion of bonding layer being made up of the glass material that the thermal coefficient of expansion than metal material is little.
In this case, the operation of clad being preferably formed as being made up of the oxide film thereon of Cr has: at moistening hydrogen gas Under the temperature conditions of less than 1150 DEG C, the Cr of metal base is preferentially made to aoxidize, thus, in Metal Substrate under atmosphere and more than 1000 DEG C The operation of the clad being made up of the oxide film thereon of Cr is preferentially formed on the surface of material.According to such composition, it is possible to reliably The thickness of the clad being fully made up of the oxide film thereon guaranteeing Cr.
Manufacturer at the above-mentioned hermetic sealing cap material having and preferentially forming the clad being made up of the oxide film thereon of Cr In method, preferably preferentially form the operation of the clad being made up of the oxide film thereon of Cr, have: being set greater than at partial pressure of oxygen can Oxidation of Fe and the dividing potential drop of Ni and less than under the moistening hydrogen atmosphere of the dividing potential drop that can aoxidize Cr, preferentially form by the oxidation quilt of Cr The operation of the clad that film is constituted.According to such composition, the most only make Cr preferential oxidation, therefore, it is possible to more reliably the most really Protect the thickness of the clad being made up of the oxide film thereon of Cr formed on the surface of metal base.
Accompanying drawing explanation
Fig. 1 is the axonometric chart of the structure of the hermetic sealing cap material of the first embodiment representing the present invention.
Fig. 2 is the sectional view of the 300-300 line along Fig. 1.
Fig. 3 is the axonometric chart of the structure of the electronic unit storage container of the first embodiment representing the present invention.
Fig. 4 is the sectional view of the 400-400 line along Fig. 3.
Fig. 5 is the sectional view of the manufacture process of the hermetic sealing cap material of the first embodiment for the present invention is described.
Fig. 6 is the cross section of the manufacture process of the electronic unit storage container of the first embodiment for the present invention is described Figure.
Fig. 7 is the experiment of the MEASURING THE THERMAL EXPANSION COEFFICIENT representing that the effect of the first embodiment for confirming the present invention carries out The table of result.
Fig. 8 is the experiment of the MEASURING THE THERMAL EXPANSION COEFFICIENT representing that the effect of the first embodiment for confirming the present invention carries out The curve chart of result.
Fig. 9 is the experiment of the MEASURING THE THERMAL EXPANSION COEFFICIENT representing that the effect of the first embodiment for confirming the present invention carries out The curve chart of result.
Figure 10 is that the thickness of the oxide film thereon layer representing that the effect of the first embodiment for confirming the present invention carries out is surveyed The table of fixed experimental result.
Figure 11 is that the thickness of the oxide film thereon layer representing that the effect of the first embodiment for confirming the present invention carries out is surveyed The table of fixed experimental result.
Figure 12 is the experiment side of the wettability determination representing that the effect of the first embodiment for confirming the present invention carries out The sectional view of method.
Figure 13 is the experiment side of the wettability determination representing that the effect of the first embodiment for confirming the present invention carries out The sectional view of method.
Figure 14 is the experiment knot of the wettability determination representing that the effect of the first embodiment for confirming the present invention carries out The chart of fruit.
Figure 15 is the experiment knot of the wettability determination representing that the effect of the first embodiment for confirming the present invention carries out The chart of fruit.
Figure 16 is the experiment knot of the wettability determination representing that the effect of the first embodiment for confirming the present invention carries out The chart of fruit.
Figure 17 is the experiment knot of the wettability determination representing that the effect of the first embodiment for confirming the present invention carries out The chart of fruit.
Figure 18 is the sectional view of the structure of the hermetic sealing cap material representing second embodiment of the present invention.
Figure 19 is the reality of the MEASURING THE THERMAL EXPANSION COEFFICIENT that expression is carried out for confirming the effect of second embodiment of the present invention Test the table of result.
Figure 20 is the reality of the MEASURING THE THERMAL EXPANSION COEFFICIENT that expression is carried out for confirming the effect of second embodiment of the present invention Test the curve chart of result.
Figure 21 is the reality of the MEASURING THE THERMAL EXPANSION COEFFICIENT that expression is carried out for confirming the effect of second embodiment of the present invention Test the curve chart of result.
Detailed description of the invention
Hereinafter, the embodiment present invention embodied is described based on accompanying drawing.
(the first embodiment)
First, see figures.1.and.2, the structure of the hermetic sealing cap material 1 of first embodiment of the present invention is described.
As it is shown in figure 1, the hermetic sealing cap material 1 of the first embodiment, by covering 10 and covering (Z1 on 10 upper surface 10a On the surface of side) glassy layer 11 that formed constitutes.Lid 10 is to have length L1 of about 2.4mm in X-direction, have about in the Y direction Length L2 of 1.9mm and there is the cuboid of thickness t1 of about 0.1mm in Z-direction.Wherein, what glassy layer 11 was the present invention " connects Close layer " example.
Glassy layer 11, the end being formed along covering the upper surface 10a of 10 is that much the same width W(is with reference to Fig. 2), Z-direction has the thickness t2 of about 0.05mm.This glassy layer 11 to receive the upper of the framework 32 of component 30 with electronic unit described later Surface 32a(is with reference to Fig. 4) corresponding mode, the end along the upper surface 10a of lid 10 is formed as frame-shaped.
It addition, glassy layer 11, by V2O5-P2O5-TeO-Fe2O3The V system low-melting glass without Pb constituted is constituted.Constitute For the thermalexpansioncoefficientα 1 of the V system low-melting glass of this glassy layer 11, the temperature range of less than about 250 DEG C more than about 30 DEG C In, about 70 × 10-7/℃.It addition, V system low-melting glass is configured to glass transition temperature is about 285 DEG C.Additionally, vitrification Transition temperature is the temperature that the thermal coefficient of expansion of V system low-melting glass changes rapidly, temperature model more than glass transition temperature Thermal coefficient of expansion (about 140 × 10 in enclosing-7/ DEG C), more than the thermal expansion system in the temperature range below glass transition temperature Number α 1(about 70 × 10-7/ DEG C).It addition, constitute glassy layer 11 V system low-melting glass seal temperature constitute be about 370 DEG C with Upper less than about 400 DEG C.
It addition, constitute the V system low-melting glass of glassy layer 11, it is configured to the inside suppressing hydrone to invade crystalline texture. Thus, glassy layer 11 has moisture-proof (resistance to water).
As in figure 2 it is shown, the oxide film thereon that lid 10 is formed by metal base 12 and the substantially entire surface of encirclement metal base 12 Layer 13 and constitute.This oxide film thereon layer 13 upper surface is formed with glassy layer 11.It addition, metal base 12, by containing about 42 Fe system alloy (42Ni-(2～6) the Cr-Fe alloy of more than Ni of quality %, about 2 mass % Cr and Fe below about 6 mass %) structure Become.Additionally, metal base 12 preferably by containing the Cr below more than about 3 mass % about 6 mass % Fe system alloy (42Ni-(3～ 6) Cr-Fe alloy) constitute.Wherein, oxide film thereon layer 13 is the example of " clad " of the present invention.
Here, in the first embodiment, the temperature range of less than about 250 DEG C more than about 30 DEG C, constitute metal base 12 The thermalexpansioncoefficientα 2 of Fe system alloy be preferably from about 55 × 10-7/ DEG C more than about 75 × 10-7/ DEG C below.That is, about 30 DEG C with In the temperature range of upper less than about 250 DEG C, the thermalexpansioncoefficientα 1 of glassy layer 11 and the thermalexpansioncoefficientα 2 of metal base 12 are excellent Be full foot-15 × 10-7≤α2-α1≤5×10-7Relation.Its result, the temperature range of less than about 250 DEG C more than about 30 DEG C In, it is configured to glassy layer 11 and is not likely to produce, with metal base 12, the stress caused because thermal expansion is different.
It addition, in the first embodiment, oxide film thereon layer 13, mainly by Cr2O3Tunicle constitute, and have in z-direction There is the thickness t3 of below more than about 0.3 μm about 1.2 μm.It addition, oxide film thereon layer 13, by the Fe system alloy to metal base 12 In the Cr that contains aoxidize on the surface of metal base 12 and formed.
Then, with reference to Fig. 3 and Fig. 4, the ministry of electronics industry to the hermetic sealing cap material 1 of the first embodiment using the present invention The structure of part storage container 100 illustrates.
As shown in Figure 3 and Figure 4, the electronic unit storage container 100 of the first embodiment, have and received quartz crystal 20(is with reference to Fig. 4) the electronic unit storage structure that sealed by the glassy layer 11 of above-mentioned hermetic sealing cap material 1 of component 30.This Time, hermetic sealing cap material 1 is configured that the upper surface 10a of the lid 10 of hermetic sealing cap material 1 is in downside (Z3 side).Wherein, water Crystal oscillator 20 is an example of " electronic unit " of the present invention.
Electronic unit storage component 30, by the Al as ceramic material2O3Constitute, and, from the point of view of plane, have in X-direction There is length L3 of about 2.5mm and there is length L4 of about 2.0mm in the Y direction.It addition, electronic unit storage component 30 is by pottery material Therefore material composition has insulating properties.It addition, more than about 30 DEG C in the temperature range of less than 250 DEG C, constitute electronic unit storage The Al of component 302O3Thermalexpansioncoefficientα 3 be about 65 × 10-7/℃.That is, the temperature model of less than about 250 DEG C more than about 30 DEG C In enclosing, the thermalexpansioncoefficientα 1(about 70 × 10 of glassy layer 11-7/ DEG C) and the thermalexpansioncoefficientα 3 of electronic unit storage component 30 full Foot 0≤α 1-α 3(=about 5 × 10-7/ DEG C)≤10 × 10-7Relation.Its result, is configured to more than about 30 DEG C less than about 250 DEG C Temperature range in, glassy layer 11 and electronic unit storage component 30 is not likely to produce the stress caused because thermal expansion is different.
It addition, electronic unit storage component 30, as shown in Figure 4, including the bottom 31 of Z3 side and the upper surface from bottom 31 The surrounding in (face of Z4 side) is by the frame portion 32 formed in the way of the extension of Z4 direction.It addition, in electronic unit storage component 30, logical Cross and surrounded by bottom 31 and frame portion 32 and be formed with recess 33.This recess 33, is formed as up (Z4 side) and has peristome, recessed On the upper surface (face of Z4 side) of the bottom 31 in portion 33, installing quartz crystal 20 via protruding 40, thus, quartz crystal 20 is received It is contained in recess 33.
It addition, the lid 10 of hermetic sealing cap material 1, via glassy layer 11, with the framework 32 of electronic unit storage component 30 Upper surface 32a engage.Specifically, the glassy layer 11 of the hermetic sealing cap material 1 of fusing is to be arranged in the upper table of framework 32 The state of face 32a is cooled, and thus, the lid 10 of hermetic sealing cap material 1 engages with electronic unit storage component 30.Thus, electricity Subassembly storage container 100 is sealed.Here, received the recess of component 30 by the electronic unit being accommodated with quartz crystal 20 33, the space that the lid 10 of hermetic sealing cap material 1 and glassy layer 11 are constituted, is configured to have bubble-tight state (substantial vacuum State).Thereby, it is possible to the change (deterioration) of the vibration characteristics etc. of suppression quartz crystal 20.
It addition, the thermalexpansioncoefficientα 2 of above-mentioned metal base 12 is according to the thermalexpansioncoefficientα 3 of electronic unit storage component 30 Determine with the relation of the thermalexpansioncoefficientα 1 of glassy layer 11.That is, receive at electronic unit due to the thermalexpansioncoefficientα 1 of glassy layer 11 Receive the thermalexpansioncoefficientα more than 3 of component 30, so, component 30 side is received for the electronic unit of glassy layer 11 and does not apply stress Or somewhat apply tensile stress.Here, meet-15 × 10 with the thermalexpansioncoefficientα 2 of metal base 12-7≤α2-α1≤5× 10-7The mode of relation constitute metal base 12, thereby, it is possible to do not apply stress in lid 10 side of glassy layer 11 or somewhat execute Add tensile stress.Its result, even if in the case of glassy layer 11 is applied stress, also receives structure at lid 10 with electronic unit The glassy layer 11 of configuration between part 30, applies from lid 10 and the tensile stress of electronic unit storage both components 30, therefore, i.e. Make to be to be ruptured the glassy layer 11 that the V system low-melting glass of (slight crack) is constituted by generation easy to tensile stress, it is also difficult to produce broken Split.
Then, with reference to Fig. 1～Fig. 6, the manufacture process of the electronic unit storage container 100 of the first embodiment is carried out Explanation.
First, prepare as depicted in figs. 1 and 2 by 42Ni-(2～6) metal base 12 that constitutes of Cr-Fe alloy.Then, As it is shown in figure 5, relative to metal base 12, in dew point is about the moistening hydrogen atmosphere of 30 DEG C, and more than about 900 DEG C about Under the temperature conditions of less than 1150 DEG C, carry out the oxidation processes (preferential oxidation of Cr) of about 30 minutes.Additionally, temperature conditions is preferred It is about more than 1000 DEG C less than about 1150 DEG C.Now, the dew point of hydrogen is about 30 DEG C, therefore, and the oxygen in moistening hydrogen atmosphere Dividing potential drop less than can Oxidation of Fe and the dividing potential drop of Ni, and on the other hand, more than the dividing potential drop that can aoxidize Cr.Thus, at metal base On the surface of 12, not Oxidation of Fe and Ni and only preferential oxidation Cr.Its result, is formed main in the substantially entire surface of metal base 12 By Cr2O3Constitute has the thickness t3(of below more than about 0.3 μm about 1.2 μm with reference to Fig. 2) oxide film thereon layer 13.
Then, as depicted in figs. 1 and 2, along the end of the upper surface (the upper surface 10a of lid 10) of oxide film thereon layer 13, The paste of the coating V system low-melting glass without Pb on the upper surface of oxide film thereon layer 13.Then, the temperature of about 410 DEG C Under the conditions of be fired, thus, remove the binding agent in the paste of V system low-melting glass.Thus, it is fabricated along covering the upper table of 10 The end of face 10a is formed with the hermetic sealing cap material 1 of glassy layer 11.
Additionally, as shown in Figure 4, prepare to be accommodated with the electronic unit storage component 30 of quartz crystal 20 in recess 33.So After, hermetic sealing cap material 1 is arranged on electronic unit storage component 30 so that the glassy layer 11 of hermetic sealing cap material 1 It is positioned at the upper surface 32a of the framework 32 of electronic unit storage component 30.Then, as shown in Figure 6, with by hermetic sealing cap material 1 Be configured at electronic unit storage component 30 state under, be positioned in vacuum drying oven 2, under vacuum conditions, and about 370 DEG C with Under the temperature conditions of upper less than about 400 DEG C, glassy layer 11 is made to melt.
Afterwards, by cooling hermetic sealing cap material 1 and electronic unit storage component 30, as shown in Figure 4, via glassy layer 11, the framework 32 upper surface 32a of the lid 10 of hermetic sealing cap material 1 with electronic unit storage component 30 is engaged.Here, from The set temperature (about 300 DEG C) that the lid 10 of hermetic sealing cap material 1 starts to engage with electronic unit storage component 30 is to constituting glass The temperature range of the glass transition temperature (about 285 DEG C) of the V system low-melting glass of glass layer 11 is (more than glass transition temperature Temperature range) in, with the thermalexpansioncoefficientα 2(about 55 × 10 of metal base 12-7/ DEG C more than about 75 × 10-7/ DEG C below) and electricity The thermalexpansioncoefficientα 3(about 65 × 10 of subassembly storage component 30-7/ DEG C below) compare, the thermal coefficient of expansion of glassy layer 11 is (about 140×10-7/ DEG C) bigger.But, the temperature range more than glass transition temperature, glassy layer 11 has mobility, therefore, Lid 10(metal base 12), glassy layer 11 and electronic unit storage component 30 in, will not occur because thermal coefficient of expansion difference is made The stress become.Additionally, the temperature range (temperature ranges of more than about 30 DEG C less than about 250 DEG C) below glass transition temperature In, glassy layer 11, lid 10 are configured to be difficult to produce the stress caused because thermal expansion is different with electronic unit storage component 30, because of This, after cooling, in lid 10, glassy layer 11 and electronic unit storage component 30, the stress of savings is little.
It addition, by carrying out engaging (sealing) under vacuum conditions, make to be accommodated with the electronic unit storage of quartz crystal 20 The space that the recess 33 of component 30, the lid 10 of hermetic sealing cap material 1 and glassy layer 11 are constituted, the most bubble-tight for having State (substantial vacuum state).Additionally, in order to make the space sealing being made up of with glassy layer 11 recess 33, lid 10 become more reliably Have under bubble-tight state, the preferably temperature conditions more than about 380 DEG C and make glassy layer 11 fusing seal.It addition, it is logical Cross and make glassy layer 11 melt under the temperature conditions of about 400 DEG C and seal, it is possible to reduce heat when sealing to quartz crystal 20 Impact.So, the electronic unit storage container 100 after the gas-tight seal shown in Fig. 3 is manufactured.
In first embodiment, as it has been described above, hermetic sealing cap material 1 possesses: formed on the surface of metal base 12 Main by Cr2O3Tunicle constitute oxide film thereon layer 13, on the surface of oxide film thereon layer 13 formed has by V2O5- P2O5-TeO-Fe2O3The glassy layer 11 of the V system low-melting glass without Pb constituted.Thus, oxide film thereon layer 13 is constituted Cr2O3Tunicle and constitute glassy layer 11 V system low-melting glass can be the most closely sealed, therefore, metal base 12 and electronic unit Storage component 30 can be sufficiently engaged with.Thus, the V system low-melting glass without Pb is used, it is possible to substantially ensure that electronic unit is received Receive by the air-tightness of container 100.It addition, hermetic sealing cap material 1 possesses by 42Ni-(2～6) metal that constitutes of Cr-Fe alloy Base material 12, thus, compared with the situation using ceramic material in base material, it is possible to reduce the airtight sealing thickness t1 of lid material 1, Therefore, it is possible to the suppression electronic unit storage maximization of container 100.Additionally, metal base 12 is by 42Ni-(2～6) Cr-Fe conjunction Gold is constituted, and thus, can easily be formed by Cr on the surface of metal base 122O3Tunicle constitute oxide film thereon layer 13.
It addition, in the first embodiment, as it has been described above, by being configured to the temperature of less than about 250 DEG C more than about 30 DEG C In scope, the thermalexpansioncoefficientα 1 of glassy layer 11 and the thermalexpansioncoefficientα 2 of metal base 12 meet-15 × 10-7≤α2-α1≤5 ×10-7Relation, thus when temperature when engaging with glassy layer 11 from metal base 12 reduces temperature, it is possible to reduce by V system The stress produced in the glassy layer 11 that low-melting glass is constituted, therefore, it is possible to the glassy layer that suppression is made up of V system low-melting glass Produce in 11 and rupture (slight crack).Additionally, by the thermalexpansioncoefficientα 1 and the thermal expansion of metal base 12 that are configured to glassy layer 11 Factor alpha 2 meets-15 × 10-7The relation of≤α 2-α 1, it is possible to suppress to be easier to tensile stress is produced break compared to compression stress Split, it is possible to suppress the tensile stress that the V system low-melting glass constituting glassy layer 11 is applied excessive.
It addition, in the first embodiment, as it has been described above, the thickness t3 of oxide film thereon layer 13 is about more than 0.3 μm about 1.2 μm Hereinafter, thereby, it is possible to substantially ensure that the thickness t3 of oxide film thereon layer 13, therefore, it is possible to make the Cr of composition oxide film thereon layer 132O3 Tunicle with constitute glassy layer 11 V system low-melting glass the most closely sealed.
It addition, in the first embodiment, as it has been described above, by being configured to metal base 12 by 42Ni-(2～6) Cr-Fe conjunction Gold is constituted, it is possible to be reliably formed by Cr in the substantially entire surface of metal base 122O3Tunicle constitute oxide film thereon layer 13.This Outward, it is possible to suppression increases because of the thermalexpansioncoefficientα 2 of the metal base 12 that Cr surplus content causes, and can suppress metal base The thermalexpansioncoefficientα 2 of 12 and the significant difference of the thermalexpansioncoefficientα 1 of glassy layer 11.Thereby, it is possible to suppression at glassy layer 11 or Person's metal base 12 produces by rupturing that the difference of thermal expansion causes.It addition, by metal base 12 containing 42 mass % Ni, it is possible to reduce the thermalexpansioncoefficientα 2 of metal base 12, thereby, it is possible to make the thermalexpansioncoefficientα 2 of metal base 12 reliably Thermal coefficient of expansion close to the glassy layer 11 being made up of the V system low-melting glass less than the thermal coefficient of expansion of common metal material α1.It is as a result, it is possible to suppress further to produce by rupturing that the difference of thermal expansion causes in glassy layer 11.
It addition, in the first embodiment, as it has been described above, by being configured to metal base 12 by 42Ni-(2～6) Cr-Fe conjunction Gold is constituted, and makes the thermalexpansioncoefficientα 1 of glassy layer 11 and the thermalexpansioncoefficientα 2 of metal base 12 reliably meet-15 × 10-7≤ α2-α1≤5×10-7Relation, therefore, it is possible to reliably suppress the glassy layer 11 being made up of V system low-melting glass produces to rupture.
It addition, in the first embodiment, as it has been described above, by making oxide film thereon layer 13 surround the most whole of metal base 12 Face and formed, from only any one face in two surfaces of metal base 12 formed oxide film thereon layer 13 situation different, energy Enough prevent from being formed glassy layer 11 on the surface of metal base 12 being formed without oxide film thereon layer 13 by mistake.Additionally, with only at gold The part belonging to base material 12 forms the situation difference of oxide film thereon layer 13, it is not necessary to when forming oxide film thereon layer 13 to Metal Substrate A part for material 12 is sheltered.Thereby, it is possible to easily form oxide film thereon layer 13.Additionally, due to make by having corrosion proof Cr2O3The oxide film thereon layer 13 constituted surrounds the substantially entire surface of metal base 12 and is formed, it is possible to improve metal base 12 Corrosion resistance.
It addition, in the first embodiment, as it has been described above, by being configured to the temperature of less than about 250 DEG C more than about 30 DEG C In scope, the thermalexpansioncoefficientα 1(about 70 × 10 of glassy layer 11-7/ DEG C) and the thermalexpansioncoefficientα 3 of electronic unit storage component 30 (about 65 × 10-7/ DEG C) meet 0≤α 1-α 3(=about 5 × 10-7)≤10 × 10-7Relation, from engaging glassy layer 11 and electronics When set temperature (about 300 DEG C) during member storage component 30 makes temperature decline, it is possible to reduction is made up of V system low-melting glass The stress produced in glassy layer 11, therefore, it is possible to suppress to produce in the glassy layer 11 being made up of V system low-melting glass to rupture.
It addition, in the first embodiment, as it has been described above, it is configured to the temperature range of less than about 250 DEG C more than about 30 DEG C In, the thermalexpansioncoefficientα 1(about 70 × 10 of glassy layer 11-7/ DEG C) and electronic unit storage component 30 thermalexpansioncoefficientα 3(about 65×10-7/ DEG C) it is 0≤α 1-α 3(=about 5 × 10-7)≤10 × 10-7, and the thermalexpansioncoefficientα 1 of glassy layer 11 and Metal Substrate The thermalexpansioncoefficientα 2(about 55 × 10 of material 12-7/ DEG C more than about 75 × 10-7/ DEG C below) be-15 × 10-7≤α2-α1≤5× 10-7.Thus, even if in the case of glassy layer 11 is applied stress, owing to receiving structure at metal base 12 and electronic unit The glassy layer 11 of configuration between part 30, applies to receive the tensile stress of both components 30 from metal base 12 and electronic unit, So, apply the situation of tensile stress to glassy layer 11 with only receiving any one of component 30 from metal base 12 and electronic unit Different, it is possible to suppression produces in glassy layer 11 and ruptures.
Additionally, in the first embodiment, as it has been described above, to metal base 12, dew point about 30 DEG C, being less than can Oxidation of Fe With the dividing potential drop of Ni and more than in the moistening hydrogen atmosphere of the dividing potential drop that can aoxidize Cr, and more than about 1000 DEG C about 1150 DEG C with Under temperature conditions under, carry out the oxidation processes (preferential oxidation of Cr) of about 30 minutes, it is possible to easily only make the preferential oxygen of Cr Change, therefore can substantially ensure that by Cr more reliably on the surface of metal base 122O3Tunicle constitute oxide film thereon layer 13 Thickness.
(embodiment)
Then, with reference to Fig. 2 and Fig. 7～Figure 17, to for confirming the thermal coefficient of expansion that the effect of the first embodiment is carried out Measure and wettability determination illustrates.
(MEASURING THE THERMAL EXPANSION COEFFICIENT)
In the mensuration of the thermal coefficient of expansion of following description, as it is shown in fig. 7, as the gold corresponding to above-mentioned first embodiment Belong to the embodiment 1～5 of base material 12, use the Fe system different containing the Cr containing ratio in the Fe system alloy of Ni with Fe of 42 mass % Alloy.
Specifically, as embodiment 1, the Fe system alloy (42Ni-2Cr-Fe alloy) of the Cr containing 2 mass % is used.Separately Outward, as embodiment 2, the Fe system alloy (42Ni-3Cr-Fe alloy) of the Cr containing 3 mass % is used.It addition, as embodiment 3, use the Fe system alloy (42Ni-4Cr-Fe alloy) of the Cr containing 4 mass %.It addition, as embodiment 4, use containing 5 matter The Fe system alloy (42Ni-5Cr-Fe alloy) of the Cr of amount %.It addition, as embodiment 5, use the Fe system of the Cr containing 6 mass % Alloy (42Ni-6Cr-Fe alloy).
On the other hand, as the comparative example 1 relative to embodiment 1～5, use containing 42 mass %Ni, Fe and do not contain Cr Fe system alloy (42Ni-Fe alloy).It addition, as the reference example 1 of the metal base to the first embodiment, use on constituting State the first embodiment glassy layer 11 by V2O5-P2O5-TeO-Fe2O3The V system low-melting glass without Pb constituted.Separately Outward, as a reference example 2, use the Al of the electronic unit storage component 30 constituting above-mentioned first embodiment2O3。
And, by making the variations in temperature of each component of embodiment 1～5, comparative example 1, reference example 1 and 2, measure each The percentage elongation of component.Wherein, (length when arbitrary temp deducts the elongation of component when percentage elongation refers to arbitrary temperature The amount that datum length during room temperature (30 DEG C) obtains) value that obtains divided by the length of benchmark during room temperature.When obtaining connection room temperature Percentage elongation and the slope of straight line of percentage elongation when 250 DEG C, swollen as the heat in the temperature ranges of more than 30 DEG C less than 250 DEG C Swollen coefficient.
As shown in Figure 8, the experimental result measured as percentage elongation, by adding in 42Ni-Fe alloy (comparative example 1) Cr, it is possible to increase percentage elongation (thermal coefficient of expansion).Additionally, by the addition increasing Cr, it is possible to increase percentage elongation.
It addition, in the following temperature range of glass transition temperature (285 DEG C) of V system low-melting glass, comparative example 1 The percentage elongation of 42Ni-Fe alloy, more much smaller than the percentage elongation of V system low-melting glass (reference example 1).It addition, embodiment 1 The percentage elongation of 42Ni-2Cr-Fe alloy, again smaller than the percentage elongation of V system low-melting glass (reference example 1).On the other hand, embodiment 2 ～the 42Ni-(3 of 5～6) percentage elongation of alloy of Cr-Fe, for approximating with the percentage elongation of V system low-melting glass (reference example 1) Value.
It addition, as shown in figures 7 and 9, as thermal coefficient of expansion, more than 30 DEG C in the temperature range of less than 250 DEG C, V Be the thermalexpansioncoefficientα 1 of low-melting glass (reference example 1) be 72 × 10-7/ DEG C, Al2O3The thermalexpansioncoefficientα 3 of (reference example 2) It is 65 × 10-7/℃.Its result, it is thus identified that the thermalexpansioncoefficientα 1 and Al of V system low-melting glass (reference example 1)2O3(reference example 2) thermalexpansioncoefficientα 3 meets 0≤α 1-α 3(=7 × 10-7)≤10 × 10-7Relation.
It addition, confirm more than 30 DEG C in the temperature range of less than 250 DEG C, the heat of the 42Ni-Fe alloy of comparative example 1 is swollen Swollen factor alpha 2 is 40 × 10-7/ DEG C, than thermalexpansioncoefficientα 1(72 × 10 of V system low-melting glass (reference example 1)-7/ DEG C) the least 32×10-7/℃.That is, the metal base of the comparative example 1 being made up of 42Ni-Fe alloy in V system low-melting glass at seal temperature When (more than about 370 DEG C less than about 400 DEG C) engage, the difference (α 2-α 1) of thermal coefficient of expansion big (-32 × 10-7/ DEG C), it is therefore contemplated that Easily produce in the glassy layer being made up of the low-melting glass of v system during cooling and rupture (slight crack).
Additionally, confirm more than 30 DEG C in the temperature range of less than 250 DEG C, the 42Ni-2Cr-Fe alloy of embodiment 1 Thermalexpansioncoefficientα 2 is 56 × 10-7/ DEG C, than thermalexpansioncoefficientα 1(72 × 10 of V system low-melting glass (reference example 1)-7/ DEG C) The least by 16 × 10-7/℃.That is, the metal base of the embodiment 1 being made up of 42Ni-2Cr-Fe alloy and V system low-melting glass are close When envelope temperature engages, the difference of thermal coefficient of expansion is greatly to a certain degree (-16 × 10-7/ DEG C), it is therefore contemplated that during cooling, it is possible to The glassy layer being made up of V system low-melting glass produces and ruptures.
On the other hand, it is thus identified that more than 30 DEG C in the temperature range of less than 250 DEG C, embodiment 2～5 42Ni-(3～ 6) thermalexpansioncoefficientα 2 of Cr-Fe alloy is 62 × 10-7/ DEG C more than 74 × 10-7/ DEG C below, with the low-melting glass (reference of V system Example 1) thermalexpansioncoefficientα 1(72 × 10-7/ DEG C) meet-10 × 10-7≤α2-α1≤2×10-7Relation.That is, by 42Ni-(3 ～6) metal base of embodiment 2～5 that constitutes of Cr-Fe alloy, less has when seal temperature engages with V system low-melting glass The difference of thermal coefficient of expansion, it is therefore contemplated that produce broken in the glassy layer being made up of V system low-melting glass when can suppress cooling Split.Its result, as metal base, it is believed that preferably 42Ni-(3～6) Cr-Fe alloy.
(wettability determination)
In the wettability determination of following description, as the embodiment of the metal base 12 corresponding to above-mentioned first embodiment 6～9, use 42Ni-4Cr-Fe alloy, and as embodiment 10～13, use 42Ni-6Cr-Fe alloy.It addition, embodiment In 6～9, temperature conditions when carrying out the preferential oxidation of Cr is different, and in embodiment 10～13, carries out the preferential oxygen of Cr Temperature conditions during change is different.Wherein, the preferential oxidation of Cr, in the moistening hydrogen atmosphere that dew point is 30 DEG C, carry out 30 points Clock.
Specifically, as shown in Figure 10 and Figure 11, as embodiment 6 and 10, under the temperature conditions of 900 DEG C, carry out Cr's Preferential oxidation.It addition, as embodiment 7 and 11, carry out the preferential oxidation of Cr under the temperature conditions of 1000 DEG C.It addition, conduct Embodiment 8 and 12, carries out the preferential oxidation of Cr under the temperature conditions of 1100 DEG C.It addition, as embodiment 9 and 13,1150 DEG C temperature conditions under carry out the preferential oxidation of Cr.
Then, measure embodiment 6～13 42Ni-4(6) Cr-Fe alloy surface on formed by Cr2O3The oxygen constituted Change the thickness t3(of tunicle layer with reference to Fig. 2).
It addition, as shown in figure 12, in embodiment 6,8～10,12 and 13 by metal base 112 and oxide film thereon layer 113 The paste 114 of V system low-melting glass is coated on the surface of the lid 110 constituted.Equally, by Al2O3The lid that (reference example 2) is constituted The paste 114 of V system low-melting glass is coated on the surface of 110.Now, at 3 on the surface of lid 110, coating width W is different Paste 114.Specifically, lid 110 surface on coating width W1 be the paste 114a of 290 μm, width W2 be 400 μm Paste 114b, width W3 are the paste 114c of 460 μm.Now, the thickness t4 of paste 114a, 114b, 114c is coated with being 80 μm.
Then, it is fired under the temperature conditions of 410 DEG C, removes the binding agent in paste 114a, 114b, 114c.By This, as shown in figure 13, paste 114a, 114b, 114c(are with reference to Figure 12) respectively become glassy layer 111a, 111b, 111c.Afterwards, Measure the width W1a and thickness t4a of glassy layer 111a, the width W2a and thickness t4b of glassy layer 111b, glassy layer 111c respectively Width W3a and thickness t4c.And, obtain glassy layer 111a(111b and 111c respectively) width and thickness relative to paste 114a(114b and 114c) width and the rate of change of thickness.Now, the width (thickness) of glassy layer 111 is more than paste 114 In the case of width (thickness), rate of change is set on the occasion of, the width (thickness) of glassy layer 111 (thick less than the width of paste 114 Degree) in the case of, rate of change is set to negative value.
As shown in Figure 10, in 42Ni-4Cr-Fe alloy, embodiment 6(900 DEG C) the thickness t3 of oxide film thereon layer not enough 0.1μm.It is formed without in i.e., it is believed that oxide film thereon is in embodiment 6(900 DEG C) as sufficient thickness.On the other hand, embodiment 7 ～9(1000 DEG C, 1100 DEG C, 1150 DEG C) in, the thickness t3 of oxide film thereon layer is more than 0.3 μm.Additionally, as shown in figure 11, In 42Ni-6Cr-Fe alloy, embodiment 10～13(900 DEG C, 1000 DEG C, 1100 DEG C, 1150 DEG C) any one in, oxide film thereon The thickness t3 of layer is more than 0.3 μm.
It addition, in embodiment 6(4Cr that temperature conditions is 900 DEG C) and embodiment 10(6Cr), temperature conditions be 1000 DEG C Embodiment 7(4Cr) and embodiment 11(6Cr), temperature conditions be embodiment 8(4Cr of 1100 DEG C) and embodiment 12(6Cr), Temperature conditions is embodiment 9(4Cr of 1150 DEG C) and embodiment 13(6Cr) any one in, use 42Ni-6Cr-Fe alloy The thickness t3 of the oxide film thereon layer of embodiment 10～13 is respectively greater than the oxidation of the embodiment 6～9 using 42Ni-4Cr-Fe alloy The thickness t3 of tunicle layer.Thus, specify that in the case of temperature conditions is identical, increase Cr content, it is possible to increase oxide film thereon The thickness t3 of layer.
It addition, as shown in Figure 14 and Figure 16, it is thus identified that embodiment 6 and 10(900 DEG C) the rate of change of width, whole Glassy layer 111a, 111b and 111c are both less than-40%.Additionally, as shown in Figure 15 and Figure 17, the thickness in embodiment 6 and 10 Rate of change, is more than 0% in addition to the thickness (-2%) of the glassy layer 111a of embodiment 6.This is because embodiment 6 and embodiment In 10, oxide film thereon layer is insufficient or incompletely formed, so wettability is low, V system low-melting glass and oxide film thereon layer are Insufficient closely sealed state.It is therefore contemplated that the mass part at the glassy layer 111 of width extension swells at thickness direction.
On the other hand, as shown in Figure 14 and Figure 16, embodiment 8 and 12(1100 DEG C), embodiment 9 and 13(1150 DEG C) and ginseng Examine example 2(Al2O3The rate of change of the width in), is more than-30% in whole glassy layer 111a, 111b, 111c.Additionally, As shown in Figure 15 and Figure 17, embodiment 8 and 12, embodiment 9 and 13, the rate of change of the thickness in reference example 2, at whole glass Layer 111a, 111b, 111c are both less than-10%.Its result is thought, in embodiment 8 and 12, embodiment 9 and 13, is sufficiently formed Oxide film thereon layer, therefore, wettability is high, and V system low-melting glass and oxide film thereon layer are the most closely sealed state.Thereby, it is possible to The part suppressing the glassy layer 111 in width extension moves at thickness direction, from without swelling at thickness direction, at width Degree direction and thickness direction reduce the volume fractiion of binding agent.
I.e., it is thus identified that the temperature range more than 1000 DEG C carries out the preferential oxidation of Cr, it is possible to make V system low-melting glass and Oxide film thereon layer is the most closely sealed state, so preferably.On the other hand, in the temperature range more than 1150 DEG C, carry out Cr's Preferential oxidation, needs the equipment that thermostability is high, it is therefore contemplated that more preferably more than 1000 DEG C, the temperature range of less than 1150 DEG C is entered The preferential oxidation of row Cr.
It addition, compared to embodiment 8 and 12(1100 DEG C), embodiment 9 and 13(1150 DEG C) the rate of change of width and thickness It is the most less, it is therefore contemplated that more preferably carry out Cr's under the temperature conditions of 1150 DEG C that the rate of change of degree reduces amplitude Preferential oxidation.
(the second embodiment)
Then, with reference to Figure 18, second embodiment of the present invention is described.The hermetic sealing cap material of this second embodiment 201, different from above-mentioned first embodiment, situation about being made up of metal base 212 3 layers of composite illustrates.
The metal base 212 of the lid 210 in the hermetic sealing cap material 201 of second embodiment of the present invention, such as Figure 18 Shown in, by being arranged in the ground floor 212a of glassy layer 11 side (Z1 side), being arranged in the Z2 side of ground floor 212a (with glassy layer 11 Opposition side) second layer 212b and be arranged in third layer 212c of Z2 side (with the opposition side of glassy layer 11) of second layer 212b Engage and formed, be made up of so-called 3 layers of composite.Additionally, ground floor 212a and third layer 212c are by containing about 42 matter Common Fe system alloy (42Ni-6Cr-Fe) of Cr and Fe measuring the Ni of %, about 6 mass % is constituted.It addition, second layer 212b by Common Fe system alloy (42Ni-Fe) of Ni, Fe containing about 42 mass % is constituted.
Additionally, the thermalexpansioncoefficientα 4 constituting the 42Ni-6Cr-Fe alloy of ground floor 212a and third layer 212c is about 75 ×10-7/℃.Additionally, the thermalexpansioncoefficientα 5 constituting the 42Ni-Fe alloy of second layer 212b is about 40 × 10-7/℃.That is, The thermalexpansioncoefficientα 4(about 75 × 10 of one layer of 212a and third layer 212c-7/ DEG C) it is more than the thermalexpansioncoefficientα 1(of glassy layer 11 about 70×10-7/ DEG C), and the thermalexpansioncoefficientα 5(about 40 × 10 of second layer 212b-7/ DEG C) less than the thermal expansion system of glassy layer 11 Number α 1.
Here, in the second embodiment, be configured to ground floor 212a, second layer 212b, the thickness of third layer 212c total (thickness of lid 210) t1 is about 0.1mm.It addition, ground floor 212a and third layer 212c have same thickness t5 in Z-direction, separately On the one hand, second layer 212b has thickness t6 in Z-direction.Here, preferred thickness t5 is thickness t6 about more than 50%.That is, first Layer 212a and third layer 212c aggregate thickness (2 × t5) be preferably lid 210 thickness t1(=2 × t5+t6) about more than 50% (about more than 0.05mm).Its result, is configured to more than about 30 DEG C in the temperature range of less than about 250 DEG C, constitutes metal base The thermalexpansioncoefficientα 2 of the composite of 212 is about 55 × 10-7/ DEG C more than about 75 × 10-7/ DEG C below.That is, it is configured to about In the temperature range of more than 30 DEG C less than about 250 DEG C, constitute the thermalexpansioncoefficientα 1(of V system low-melting glass of glassy layer 11 about 70×10-7/ DEG C) and the thermalexpansioncoefficientα 2 of the composite that constitutes metal base 212 meet-15 × 10-7≤α2-α1≤5× 10-7Relation.
Additionally, in the face of the Z1 side of ground floor 212a and side, be formed main by Cr2O3The oxide film thereon layer constituted 213a, and it is formed main by Cr in face and the side of the Z2 side of third layer 212c2O3The oxide film thereon layer 213b constituted.Should Oxide film thereon layer 213a and 213b is respectively by contained in the 42Ni-6Cr-Fe alloy of ground floor 212a and third layer 212c Cr is formed in the face of the Z1 side of ground floor 212a and the face of the Z2 side of side and third layer 212c and lateral oxidation.Additionally, Other of second embodiment are constituted, identical with above-mentioned first embodiment.
Then, with reference to Figure 18, the manufacture process of the hermetic sealing cap material 201 of second embodiment of the present invention is described.
First, the sheet material (not shown) being made up of 42Ni-Fe alloy with specific thickness is prepared.It addition, prepare by 42Ni-6Cr-Fe alloy constitute and have the board member being made up of 42Ni-Fe alloy thickness about more than 50% thickness Sheet material 2 pieces.Then, the state of the sheet material clamping being made up of 42Ni-6Cr-Fe alloy at the sheet material being made up of 42Ni-Fe alloy Under, the sheet material being made up of 42Ni-Fe alloy and a pair sheet material being made up of 42Ni-6Cr-Fe alloy are applied the pressure of regulation Engage under state.Thus, as shown in figure 18, the ground floor 212a that is made up of 42Ni-6Cr-Fe alloy, closed by 42Ni-Fe Second layer 212b and third layer 212c being made up of 42Ni-6Cr-Fe alloy that gold is constituted are connect when lamination successively Close, form the composite of 3 layers.Now, the thickness t5 of ground floor 212a and third layer 212c is the thickness of second layer 212b About more than the 50% of t6.Hereafter, by composite being cut to the shape of regulation, metal base 211 is formed.
Then, under conditions of identical with above-mentioned first embodiment, carry out the preferential oxidation of Cr, thus, at ground floor The face of the Z1 side of 212a and side are formed main by Cr2O3The oxide film thereon layer 213a constituted, and in the Z2 side of third layer 212c Face and side formed main by Cr2O3The oxide film thereon layer 213b constituted.Additionally, other of second embodiment of the present invention Manufacture process is identical with the first embodiment.
In second embodiment, as it has been described above, hermetic sealing cap material 201 possesses: shape on the surface of metal base 212 Become is main by Cr2O3Tunicle constitute oxide film thereon layer 213a and 213b and on the surface of oxide film thereon layer 213a shape The glassy layer 11 being made up of the V system low-melting glass without Pb become, thus, metal base 212 and electronic unit storage component 30(is with reference to Fig. 4) can be sufficiently engaged with.Additionally, hermetic sealing cap material 201 possesses the Metal Substrate comprising 42Ni-6Cr-Fe alloy Material 212, thus, compared with the situation using ceramic material in base material, it is possible to reduce the thickness t1 of hermetic sealing cap material 201. Additionally, comprise 42Ni-6Cr-Fe alloy by metal base 212, the surface of metal base 212 can easily be formed by Cr2O3Tunicle constitute oxide film thereon layer 213a and 213b.
It addition, in the second embodiment, as it has been described above, metal base 212 is by ground floor 212a, is arranged in ground floor The second layer 212b of the Z2 side of 212a, third layer 212c of the Z2 side being arranged in second layer 212b engage the 3 layers of composite wood formed Expecting and formed, and ground floor 212a and third layer 212c are made up of 42Ni-6Cr-Fe alloy, second layer 212b is by 42Ni-Fe Alloy is constituted, thus, with metal base 212 only compared with one layer of situation about constituting, different not by engaging thermal coefficient of expansion Congener metal material is each other, it is possible to be easily adjusted the thermalexpansioncoefficientα 2 of metal base 212.It addition, can be airtight close Envelope two surfaces of lid material 201, ground floor 212a that configuration is made up of 42Ni-6Cr-Fe alloy and third layer 212c, therefore, Can on each face on two surfaces (face of the Z1 side of ground floor 212a and the face of the Z2 side of third layer 212c) of metal base 212 Formed by Cr2O3Tunicle constitute oxide film thereon layer 213a and 213b.Thus, with only in two surfaces of metal base 212 The situation forming oxide film thereon layer on any one face is different, it is possible to prevent from being formed without the metal base 212 of oxide film thereon layer Surface on form glassy layer 11 by mistake.
It addition, in the second embodiment, as it has been described above, the ground floor 212a of metal base 212, second layer 212b and the 3rd Layer 212c is made up of the Fe system alloy of the Ni containing 42 mass %, thereby, it is possible to make ground floor 212a, second layer 212b and the 3rd The thermal coefficient of expansion of layer 212c all reduces.Thereby, it is possible to make metal base 212 thermalexpansioncoefficientα 2 can reliably close to by The thermalexpansioncoefficientα 1 of the glassy layer 11 that the V system low-melting glass that thermal coefficient of expansion is less than common metal material is constituted.Additionally, If ground floor 212a and third layer 212c are made up of common 42Ni-6Cr-Fe alloy, second layer 212b is by common 42Ni- Fe alloy is constituted, then can use the Fe system alloy being readily available, at the metal base in the region corresponding to forming glassy layer 11 Formed by Cr on the surface of 2122O3Oxide film thereon layer 213a and 213b that constitute of tunicle, and make the heat of metal base 212 swollen Swollen factor alpha 2 is close to the thermalexpansioncoefficientα 1 of the glassy layer 11 being made up of V system low-melting glass.
It addition, in the second embodiment, as it has been described above, it is configured to the thermal coefficient of expansion of ground floor 212a and third layer 212c α 4(about 75 × 10-7/ DEG C) more than the thermalexpansioncoefficientα 1(about 70 × 10 of glassy layer 11-7/ DEG C), and the heat of second layer 212b Coefficient of expansion α 5(about 40 × 10-7/ DEG C) less than the thermalexpansioncoefficientα 1 of glassy layer 11, thus, by adjusting ground floor 212a's Thickness t5, the thickness t6 of second layer 212b and the thickness t5 of third layer 212c, it becomes possible to make metal base 212 as overall heat Coefficient of expansion α 2 is close to the thermalexpansioncoefficientα 1 of glassy layer 11.
It addition, in the second embodiment, as it has been described above, it is configured to the aggregate thickness (2 of ground floor 212a and third layer 212c × t5) lid 210 thickness t1(=2 × t5+t6) about more than 50%, thus, the thermalexpansioncoefficientα 1 of glassy layer 11 and metal The thermalexpansioncoefficientα 2 of base material 212 disclosure satisfy that-15 × 10-7≤α2-α1≤5×10-7Relation, therefore, it is possible to reliably suppress The glassy layer 11 being made up of V system low-melting glass produces and ruptures (crack).Additionally, other effects of the second embodiment are with upper State the first embodiment identical.
(embodiment)
Then, with reference to Figure 18～Figure 21, in order to confirm the MEASURING THE THERMAL EXPANSION COEFFICIENT that the effect of the second embodiment is carried out Illustrate.
(MEASURING THE THERMAL EXPANSION COEFFICIENT)
In the MEASURING THE THERMAL EXPANSION COEFFICIENT of following description, as shown in figure 19, as the Metal Substrate with above-mentioned second embodiment The embodiment 14～18 of material 212 correspondence, use have be made up of 42Ni-6Cr-Fe alloy ground floor 212a, closed by 42Ni-Fe Second layer 212b that gold is constituted and the 3 layers of composite of third layer 212c being made up of 42Ni-6Cr-Fe alloy, and ground floor The total of the thickness of 212a and the thickness of third layer 212c (2 × t5(is with reference to Figure 18)) relative to the ratio of thickness t1 of lid 210 (thickness of slab ratio) is different.
Specifically, as embodiment 14, the total (2 × t5) of ground floor 212a and the thickness of third layer 212c is set to The 12.5% of the thickness t1 of lid 210, by the thickness t6(of second layer 212b with reference to Figure 18) it is set to cover the 87.5% of the thickness t1 of 210. It addition, as embodiment 15, the total (2 × t5) of thickness is set to the 25% of thickness t1, thickness t6 is set to the 75% of thickness t1. It addition, as embodiment 16, the total (2 × t5) of thickness is set to the 50% of thickness t1, and thickness t6 is set to thickness t1's 50%.It addition, as embodiment 17, the total (2 × t5) of thickness is set to the 67% of thickness t1, thickness t6 is set to thickness t1's 33%.It addition, as embodiment 18, the total (2 × t5) of thickness is set to the 75% of thickness t1, thickness t6 is set to thickness t1's 25%。
It addition, as the comparative example 1 relative to embodiment 14～18, use the comparative example 1 with above-mentioned first embodiment The identical metal base being only made up of 42Ni-Fe alloy.That is, as comparative example 1, the thickness of 42Ni-6Cr-Fe alloy is used The metal base that thickness of slab ratio is 0% of t5.It addition, as comparative example 3, use the embodiment 5 with above-mentioned first embodiment same The metal base being only made up of 42Ni-6Cr-Fe alloy of sample.That is, as comparative example 3, the thickness of 42Ni-6Cr-Fe alloy is used The metal base that thickness of slab ratio is 100% of degree t5.It addition, identical with the first embodiment, 1 use V system eutectic as a reference example Point glass, and 2 use Al as a reference example2O3。
And, with the method as the MEASURING THE THERMAL EXPANSION COEFFICIENT of above-mentioned first embodiment, obtain embodiment 14～18, The heat of the temperature range of comparative example 1 and 3, the percentage elongation of each component of reference example 1 and 2 and more than 30 DEG C less than 250 DEG C The coefficient of expansion.
As shown in figure 20, the experimental result measured as percentage elongation, by increasing the thickness ratio of 42Ni-6Cr-Fe alloy Rate, it is possible to increase percentage elongation (thermal coefficient of expansion).
It addition, in the following temperature range of glass transition temperature (285 DEG C) of V system low-melting glass, embodiment 14 (12.5%) and embodiment 15(25%) percentage elongation less than the percentage elongation of V system low-melting glass (reference example 1).On the other hand, real Execute example 16～18 and comparative example 3(50%～100%) percentage elongation, for approximating with the percentage elongation of V system low-melting glass (reference example 1) Value.
It addition, as shown in Figure 19 and Figure 21, it is thus identified that as thermal coefficient of expansion, the temperature of less than 250 DEG C more than 30 DEG C In scope, embodiment 14(12.5%) thermalexpansioncoefficientα 2 be 45 × 10-7/ DEG C, than the heat of V system low-melting glass (reference example 1) Coefficient of expansion α 1(72 × 10-7/ DEG C) the least by 27 × 10-7/℃.It addition, confirm embodiment 15(25%) thermalexpansioncoefficientα 2 It is 51 × 10-7/ DEG C, than thermalexpansioncoefficientα 1(72 × 10 of V system low-melting glass (reference example 1)-7/ DEG C) the least by 21 × 10-7/ ℃.That is, at seal temperature (more than about 370 DEG C less than about 400 DEG C) interengaging embodiment 14(12.5%) and embodiment 15(25%) Metal base, during with V system low-melting glass, the difference (α 2-α 1) of thermal coefficient of expansion is big to a certain degree (-27(21) × 10-7/ DEG C), rupture (slight crack) it is therefore contemplated that may produce in the glassy layer being made up of V system low-melting glass during cooling.
On the other hand, it is thus identified that more than 30 DEG C in the temperature range of less than 250 DEG C, embodiment 16～18 and comparative example 3 The thermalexpansioncoefficientα 2 of (50%～100%) is 58 × 10-7/ DEG C more than 74 × 10-7/ DEG C below, with the low-melting glass (reference of V system Example 1) thermalexpansioncoefficientα 1(72 × 10-7/ DEG C), meet-14 × 10-7≤α2-α1≤2×10-7Relation.That is, temperature is being sealed When the metal base of degree interengaging embodiment 16～18 is with V system low-melting glass, almost without the difference of thermal coefficient of expansion, it is taken as that Can suppress to produce in the glassy layer being made up of V system low-melting glass to rupture when cooling.Its result, as metal base, Consider the thickness of slab ratio of 42Ni-6Cr-Fe alloy is preferably set to more than the 50% of metal base (lid).
Additionally, embodiment of disclosure and embodiment, it should it is understood to all be exemplary rather than limiting.The present invention Scope represent but by the Range Representation of claim not by the explanation of the above-described embodiment and examples, and Also include all changes that the scope with claim is equal in the meaning and scope.
Such as, above-mentioned first embodiment, metal base 12 illustrates by 42Ni-(2～6) example that constitutes of Cr-Fe alloy In son, and above-mentioned second embodiment, illustrate metal base 212 by first by being made up of 42Ni-6Cr-Fe alloy Layer 212a, the second layer 212b being made up of 42Ni-Fe alloy and third layer 212c being made up of 42Ni-6Cr-Fe alloy engage The example that the composite arrived is constituted, but the invention is not restricted to this.It is not must that the present invention constitutes the metal material of metal base Must be containing Ni, containing Cr.
It addition, in above-mentioned first and second embodiments, illustrate and also form master beyond the part of configuration glassy layer 11 Will be by Cr2O3Tunicle constitute oxide film thereon layer 13(213a and 213b) example, but the invention is not restricted to this.The present invention In, can be only at the part formation oxide film thereon layer of configuration glassy layer.
It addition, in above-mentioned second embodiment, illustrate metal base 212 by ground floor 212a, second layer 212b and Three layers of 212c engage the example that the 3 layers of composite obtained are constituted, but the invention is not restricted to this.For example, it is also possible to by 42Ni- The ground floor that 6Cr-Fe alloy is constituted engages the 2 layers of composite obtained and constitutes with the second layer being made up of 42Ni-Fe alloy.This Outward, it is also possible to engaged, by more than 4 layers, the composite obtained and constitute.
It addition, in above-mentioned second embodiment, illustrate ground floor 212a and third layer 212c by having same composition The example that 42Ni-6Cr-Fe alloy is constituted, but the invention is not restricted to this.In the present invention, the composition of ground floor 212a and the 3rd The composition of layer 212c can be different.Now, the Cr containing ratio of ground floor 212a of glassy layer 11 side it is arranged in preferably in about 3 matter Amount more than %.
It addition, in above-mentioned first and second embodiments, illustrate glassy layer 11 by V2O5-P2O5-TeO-Fe2O3And do not contain The example that the V system low-melting glass of Pb is constituted, but the invention is not restricted to this.In the present invention, glassy layer can also be V system eutectic The glass material without Pb beyond some glass.Now, by using the glass of fusing under the temperature conditions below about 400 DEG C Material, it is possible to reduce the impact on quartz crystal of heat when sealing.
It addition, in above-mentioned first and second embodiments, illustrate quartz crystal 20 at electronic unit storage container 100 The example of middle storage, but the invention is not restricted to this, such as SAW filter (surface elastic wave filter) can be accommodated in electricity In subassembly storage container.

Claims (13)

1. a hermetic sealing cap material, it is characterised in that:
Its including being made up of ceramic material, receive the electricity of component (30) for the electronic unit of housing electronic parts (20) The subassembly storage hermetic sealing cap material (1,201) used in container (100), possesses:
Comprise the metal base (12,212) of the metal material at least containing Cr；
The clad (13,213a, 213b) being made up of the oxide film thereon of Cr formed on the surface of described metal base；With
Formed on the surface of described clad is made up of the glass material without Pb and is formed with described bag for engaging The described metal base of coating receives the bonding layer (11) of component with described electronic unit；
Described metal base is made up of the composite including ground floor, the second layer and third layer,
Described ground floor, is arranged in described tielayer side, at least contains Cr；
The described second layer, is arranged in described ground floor with described bonding layer opposition side, comprises different from described ground floor Metal material；
Third layer (212c), is arranged in the described second layer with described ground floor opposition side, at least contains Cr；
Described ground floor and described third layer are closed by the Fe system containing Cr and Fe below more than Ni, 3 mass % 6 mass % Gold is constituted,
The aggregate thickness of described ground floor and described third layer is more than the 50% of the integral thickness of described metal base.
2. hermetic sealing cap material as claimed in claim 1, it is characterised in that:
More than 30 DEG C in the temperature range of less than 250 DEG C, the thermalexpansioncoefficientα of described bonding layer 1 (/ DEG C) and described Metal Substrate The thermalexpansioncoefficientα 2 of material (/ DEG C) meet-15 × 10-7≤α2-α1≤5×10-7Relation.
3. hermetic sealing cap material as claimed in claim 1, it is characterised in that:
The thickness of described clad is more than 0.3 μm.
4. hermetic sealing cap material as claimed in claim 1, it is characterised in that:
Described clad be formed at configure described bonding layer described metal base surface on and with configure described tielayer side Opposition side described metal base surface on.
5. hermetic sealing cap material as claimed in claim 1, it is characterised in that:
The thermal coefficient of expansion of described ground floor is more than the thermal coefficient of expansion of described bonding layer, and the thermal coefficient of expansion of the described second layer is little Thermal coefficient of expansion in described bonding layer.
6. hermetic sealing cap material as claimed in claim 1, it is characterised in that:
Described ground floor and described third layer are constituted by 42Ni-6Cr-Fe alloy,
The described metal material of the described second layer is 42Ni-Fe alloy.
7. an electronic unit storage container (100), it is characterised in that:
Possess hermetic sealing cap material (1,201) and electronic unit storage component (30), wherein,
Described hermetic sealing cap material (1,201), comprising: have the metal material at least containing Cr metal base (12, 212)；The clad (13,213a, 213b) being made up of the oxide film thereon of Cr formed on the surface of described metal base；With The bonding layer (11) being made up of the glass material without Pb formed on the surface of described clad；And,
Described electronic unit storage component (30), it is via described bonding layer and the described metal base being formed with described clad Engage, and be made up of ceramic material, for housing electronic parts (20)；
Described metal base is made up of the composite including ground floor, the second layer and third layer,
Described ground floor, is arranged in described tielayer side, at least contains Cr；
The described second layer, is arranged in described ground floor with described bonding layer opposition side, comprises different from described ground floor Metal material；
Third layer (212c), is arranged in the described second layer with described ground floor opposition side, at least contains Cr；
Described ground floor and described third layer are closed by the Fe system containing Cr and Fe below more than Ni, 3 mass % 6 mass % Gold is constituted,
The aggregate thickness of described ground floor and described third layer is more than the 50% of the integral thickness of described metal base.
8. electronic unit storage container as claimed in claim 7, it is characterised in that:
More than 30 DEG C in the temperature range of less than 250 DEG C, the thermalexpansioncoefficientα of described bonding layer 1 (/ DEG C) and the described ministry of electronics industry The thermalexpansioncoefficientα 3 of part storage component (/ DEG C) meet 0≤α 1-α 3≤10 × 10-7Relation.
9. electronic unit storage container as claimed in claim 8, it is characterised in that:
More than 30 DEG C in the temperature range of less than 250 DEG C, the thermalexpansioncoefficientα of described bonding layer 1 (/ DEG C) and the described ministry of electronics industry The thermalexpansioncoefficientα 3 of part storage component (/ DEG C) meet 0≤α 1-α 3≤10 × 10-7Relation, and, the heat of described bonding layer The thermalexpansioncoefficientα 2 of coefficient of expansion α 1 (/ DEG C) and described metal base (/ DEG C) meet-15 × 10-7≤α2-α1≤5×10-7 Relation.
10. the manufacture method for the hermetic sealing cap material described in manufacturing claims 1, it is characterised in that:
For manufacturing, it is including that the electronic unit for housing electronic parts (20) being made up of ceramic material receives component (30) the electronic unit storage hermetic sealing cap material used in container (100), this manufacture method includes:
On the surface of metal base (12,212) comprising the metal material at least containing Cr, by making described metal base Cr oxidation and form the operation of the clad (13,213a, 213b) being made up of the oxide film thereon of Cr；With
In described cover surface, formed and be made up of the glass material without Pb and be formed with described clad for engaging The operation of bonding layer (11) of described metal base and described electronic unit storage component.
The manufacture method of 11. hermetic sealing cap materials as claimed in claim 10, it is characterised in that:
Form the operation of described clad, including: at the table of the described metal base comprising the metal material with Fe system alloy On face, forming the operation of the described clad being made up of the oxide film thereon of Cr, wherein, described Fe system alloy contains Ni, 3 mass % Cr and Fe below above 6 mass %.
The manufacture method of 12. hermetic sealing cap materials as claimed in claim 11, it is characterised in that:
Form the operation of described clad being made up of the oxide film thereon of Cr, have: by under moistening hydrogen atmosphere and Under the temperature conditions of more than 1000 DEG C less than 1150 DEG C, the Cr of described metal base is preferentially made to aoxidize, and at described metal base Surface on preferentially form the operation of the described clad being made up of the oxide film thereon of Cr.
The manufacture method of 13. hermetic sealing cap materials as claimed in claim 12, it is characterised in that:
Preferentially form the operation of the described clad being made up of the oxide film thereon of Cr, have: being set smaller than at partial pressure of oxygen can Oxidation of Fe and the dividing potential drop of Ni and more than under the described moistening hydrogen atmosphere of the dividing potential drop that can aoxidize Cr, preferentially form by the oxygen of Cr Change the operation of the described clad that tunicle is constituted.
CN201180066844.0A 2011-02-07 2011-11-02 Hermetic sealing cap material, electronic unit storage container and the manufacture method of hermetic sealing cap material Expired - Fee Related CN103354950B (en)

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